STUDIES OF T H E AVAILABILITY OF TOXIC HEAVY ELEMENTS IN SOILS AND SEDIMENTS IN THE VICINITY OF A LEAD SMELTING SITE (GERMANY)

D. W. Z A C H M A N N and R. B L O C K Department of Geosciences, Technical University of Braunschweig, Pockelsstr. 4, 38106 Braunschweig, FRG (Received 19 November, 1992; accepted in final form 26 November, 1993)

Abstract. The lead smelting site near Clausthal-Zellerfeld (Harz Mountains, Germany) was in operation for 700 years. As a result of this long operating time, the soil and stream sediments in the vicinity of the site are highly contaminated due to airborne pollution and dumping of slags. The knowledge of bulk concentrations does not give sufficient information for an estimate of the hazard potential stored in the contaminated materials. Therefore, as a first step, the element speciation in the three sample populations was determined. As the extractability (availability) of the speciations varies significantly for the different elements, a second step was used to test for the availability. The investigations on the availabilities yield a very high hazard potential for lead, followed by Cu and Zn.

1. Introduction Due to industrial activities since ancient times, many soils and sediments in Middle Europe are higly polluted by heavy elements. Extremely high contaminations occur in the vicinity of mining and smelting sites. The mining industry has been active in the Harz Mountains (Germany) for more than 1000 years. Due to this long period of mining and smelting, vast areas of the Harz Mountains are highly polluted and show concentrations, especially of lead (NOWAK and Preul, 1971), which significantly exceed the tolerable limits as defined by recent jurisdiction in Western Europe (Hein and Schwedt, 1991; Bundesgesetzblatt, 1992). These limits are (mg/kg dry soil substance): Pb - 100; Cu - 60; Zn - 200; As - 20. The definition of tolerable limits concerns extractable bulk concentrations of heavy elements in soils. Two basic procedures exist for determining these concentrations. One procedure analyzes bulk concentrations after digestion of the soils and sediments with strong acids (e.g. aqua regia; procedure standardized by DIN 38 414 - 7; cf. Appendix: Analytical procedures). Generally, this procedure leaches heavy element amounts from the soils and sediments, in percentages which significantly exceed their availability in their natural environment. However, only the available concentrations are important for a pollution hazard prognosis. A second procedure measures the concentrations in an elution of water (DIN 38 414 - 4; cf. Appendix). The concentrations resulting from this procedure are too small to be useful in hazard prognoses. An estimate of the available amounts (easily extractable by natural processes) of heavy elements in soils and sediments can be obtained first by a detailed definition of their bonding forms. In the last several years, procedures have been proposed, which
Water, Air and Soil Pollution 78:317-334, 1994. @ 1994 Kluwer Academic Publishers. Printed in the Netherlands.

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D.W. ZACHMANN AND R. BLOCK

should allow the bulk of element concentrations to be discriminated into different bonding forms. These procedures can be summarized as 'sequential elution' (e.g. Tessier et al., 1979; F6rstner and Calmano, 1982; F6rstner, 1987; Gunn et al., 1988). The procedures are based on the subsequent elution by a series of solutions, each of which digests a specific bonding form, thus liberating the percentage of elements fixed in this bonding form. Of special interest are bonding forms of low stability, which show a high pollution potential for the environment. Such bonding forms are: a) adsorption, b) mineralizations of low or intermediate stability in natural environments, e.g. limonite (FeOOH). As natural substance may be composed partially from poorly defined substances (amorphous, transitional, metastable), the results of the separation procedures are strictly operational (Loring and Rantala, 1992) and should be considered at the most as an approximation of the 'true' mineralogical composition of the samples. Applied to mixtures of pure substances (i.e. carbonates, Fe-Mn-oxides, sulfides, etc.) the separation procedure described by Jakob et al. (1990) allows differentiations into reasonable mineralogical phases. As demonstrated for the example of the Fe-Mn-oxides (Fig. 1) this Jakob's method also holds for the soils and stream sediments investigated in this study. Coupled with careful observation and consideration of its limitations, the sequential elution procedure is a valuable tool for the discrimination of bonding forms, and can give a better understanding of the availability of toxic elements. However, it should be kept in mind, that different elements in the very same bonding form show different solubilities. Therefore, the definition of bonding forms by the sequential elution procedure alone does not give sufficient information on the availability of elements. The estimate of a direct and short-term hazard by heavy elements has to take into consideration the proportions of easily extractable chemical forms (speciations) in the soils. In order to quantify these proportions, a bulk elution procedure was applied. The method was originally developed tod efine the concentrations of plant available cations in soils (DIN 19 684-8; cf. Appendix), i.e. the generally easily available cations in soils. The method is based on the percolation with a Ba-chloride solution (pH = 7). It measures the availability of the elements without defining the specific bonding forms. The combination of the results of both elution procedures will give a more realistic estimate of the hazard potential of some heavy elements in different sample populations. This study takes into account only long-term 'normal' environmental processes, i.e. leaching of toxic elements by pore solutions from rocks and soils. The consequences of changes of soil pH due to acid precipitation are not considered (e.g. corrosion and dissolution of transition element carbonates).

STUDIES OF THE AVAILABILITY OF TOXIC HEAVY ELEMENTS

319

100 9080-

E: 70._m
60tO

AI

r-

404 30-

/'&'"-,i.

,."

Fe

0J 0 t-" 0 O

20100
o 1 2 Fe (forest soils)

3 4 steps of sequential elution

Mn (forest soils) ~ -~-- Fe (stream sed.) --~k-- Mn (stream sed.)

AI (forest soils)

Fig. 1. Percentagesof Fe-, Mn-, and Al-concentrationsreleasedduringseq. el.

2. Analytical procedures
The elution procedure used here follows the method as described by Jakob et al. (1990). The method is based on the evaluation of different elution methods (Tessier et al., 1979; F6rstner and Calmano, 1982; F6rstner, 1987; Gunn et al., 1988). The applied elution procedure was verified in different laboratories on industrial and naturally occurring substances with good coincidence of the results. The applied elution procedure defines the following bonding forms of elements (1. - 6.: elution steps): 1. Exchangeable cations: adsorption to soil minerals (e.g. clay minerals, carbonates, etc.). 2. Carbonate hosted cations: isomorphical substitution of carbonate hosted cations by trace cations or solid solution of carbonate forming cations (e.g. Zn in dolomite). 3. Easily reducible phase: cations substituted into amorphous oxide-hydroxidephases (Mn, Fe, AI). 4. Moderately reducible phase: cations substituted into crystalline oxide-hydroxides (Fe, A1, Mn). 5. Sulfidic and organic phase: sulfide forming elements and elements with a high affinity to organic soil substances.

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D.W. ZACHMANN AND R. BLOCK

TABLE I Procedure of sequential elution (abbreviations: amrn.ac. - ammonium acetate; Na-ac. - sodium acetate; amm. cl. - ammonium chloride; sample weight: 1 g) elution solution/ step concentr, (phase) (mol/1) 1 2 3 4 5 6 amm.ac./(1) Na-ac./(1) hydroxylamm.cl./(0.1) amm.oxalateox. acid/(0.2) a) H202 b) amm.ac./(1) aqua regia pH quan- time of tity extract. (n'd) (h) 20 20 100 100 30 100 40 2 5 12 24 2 12 2 remarks

7 5 2 3 2 7 <0

1 1 1 1 2 2 3

remarks: 1, Extractions 1--4: the samples remain in the centrifuge vessels; during the time of extraction the vessels are shaken; after extraction the solutions are centrifuged with 3600 rpm; the solution is filtered (0.45 #m). 2. Extraction 5: The residue of step 5 is transferred into a 250 ml beaker; H202 is added and the residue carefully digested on a heating plate. The solution is evaporated until nearly dry; amm.ac. is added and after shaking the solution is centrifuged. 3. Centrifuge after digestion at 120 ~

6. Residual phase: cations, which form stable mineralizations, (e.g. silicates). The sequential elution procedure is summarized in Table I. The extraction solution of each step is filtered to yield a clear solution, which is analyzed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP - OES). Hypothetically, it is expected that the elution by BaC12 releases proportions o f heavy elements which correspond at least to the concentrations extracted by step 1 in the sequential elution. Possibly, the cations bound to phases 3 and 4 are also bound by adsorption and therefore, eluted by the BaC12 method. In a first experimental approach, the application of this procedure, as described by DIN 19 684, showed that the elements are eluted in very specific amounts by the BaC12-solution. However, if the procedure is followed precisely, the eluted amounts o f elements remain in some cases far below the amounts extracted by step 1 o f the sequential elution. For example, only 45% of Zn and 30% of Pb were eluted by the BaC12-solution as compared to the amounts extracted in step 1 in the sequential elution. This difference is due to the relatively fast percolation of the

STUDIES OF THE AVAILABILITY OF TOXIC HEAVY ELEMENTS

321

BaC12-solution. The procedure was therefore modified by reducing the percolation rate to 0.2 mL/min. (Goll, 1990; Meiwes et al., 1984). The question is how far concentrations of Pb, Zn, Cu, and Cd eluted by the BaC12-solution (defined here as easily available) fit concentrations eluted by single elution steps or sums of elution steps of the sequential extraction, or whether they fit at all.

3. Preliminary investigations
In addition to the elements bound by adsorption (phase 1), some of the heavy elements bound by the reducible phases (3 and 4) might be easily available. The bulk composition of the reducible phases is predominated by Fe- and Mnoxidehydroxides. Therefore, the release (i.e. decomposition of the oxides) of Fe and Mn during the sequential elution was scrutinized (Fig. 1). As demonstrated by thermodynamic calculations in the system: Eh, pH, Fe, Mn, 02, OH- (e.g. Ball etal., 1987), under reducing conditions the reaction begins with the decomposition of the Mn-phase. Investigations on 10 stream sediments (Block and Zachmann, 1991), and 17 soil samples (Lotze, 1992) demonstrate that Mn is extracted mainly during elution step 3, whereas Fe follows in step 4 (Fig. 1). Therefore, for simplification, the easily reducible phase (step 3) will be defined in this text as Mn-oxide phase, and the moderately reducible phase (step 4) as Fe-oxide phase. The mineralogical phase analyses which were performed by Block and Zachmann (op. cit.) display a lack of Mn-mineralizations despite relatively high amounts in some of the samples (cf. Table II). This indicates that the easily reducible phase is predominated by (X-ray) amorphous Mn phases. However, the phase analyses display oxidic-hydroxidic Fe mineralizations (e.g. hematite, limonite). This indicates the decomposition of compounds of higher crystallinity during elution step 4. In addition, the analyses of the soil samples also show a significant release of A1 during elution step 4 (Fig. 1). 4. Comparison of investigations of the bonding forms of heavy elements in

different sample populations

The sequential elution procedure was applied for the determination of the bonding forms of heavy elements in forest soils (para-brown earth, soil pH 3.8-4.6), stream sediments, and slags. All samples were taken in the vicinity of the Bleihtitte (lead) smelting site near Clausthal-Zellerfeld (Harz Mountains, Germany; Fig. 2). The smelting site was in operation for 700 years. Therefore, all areas and materials in the vicinity are highly polluted by heavy elements. This is shown by the map of lead distribution in forest soils in the Bleihtitte area (Fig. 3). The mineralogical composition and the bulk concentrations of heavy elements and main elements of the analyzed materials are listed in Tables 2, 3, and 4. The

322

D.W. ZACHMANNAND R. BLOCK

TABLE II Mean concentrations of some main elements in forest soils, highly contaminated stream sediments, and slags (weight-%) materials forest soils (lc) 1.36 -t- 0.28 0.04 4- 0.03 0.02 4- 0.01 0.114-0.04 1.08 4- 0.01

element Fe Mn Ca Mg A1

forest soils (hc) 2.94 4- 0.42 0.02 4- 0.01 0.02 4- 0.01 0.124-0.05 1.20 4- 0.27

stream sediments 3.30 4- 1.10 0.40 4- 0.24 1.31 4- 0.87 0.344-0.08 0.72 4- 0.33

slags (n = 2) 12.9 0.83 0.59 0.41 0.47

forest soils: - lc: background forest soils; low concentrations of toxic elements hc: contaminated forest soils; high concentrations of toxic elements

TABLE III Mineralogical and chemical composition (bulk analyses) of the investigated forest soils in comparison to tolerable values sample Nr. 1100/12 /20 /55 1200/9 /17 /25 /55 1400/8 /15 /25 /40 mineral, compos. H, Q, Q, H, H, Q, Q, H, H, Q, Q, Q, H, M, Q, Q, M, M, Q, Q, M, M, M M Fs M M H Fs M M H Fs heavy elements Zn Pb Cu 100 90 51 110 57 72 44 95 92 71 47 300 1530 248 92 31160 5690 3400 628 1970 1730 1070 463 100 17 12 13 135 27 24 6 60 53 39 10 100

Cd 7 6 5 7 8 6 6 7 7 6 4 3

Ni 15 21 32 22 33 21 14 20 19 20 20 50

As 7 3 5 26 8 3 3 6 6 4 4 20

Se 1.1 0.9 0.5 2.5 0.9 0.7 0.4 0.3 0.2 0.1 0.5 10

tolerable values in culture soils Kloke, 1980

Abbreviations: H - humic substances, Q - quartz, M - muscovite, Fs feldspar; Concentrations in ppm (#g/g), rounded values; .../12: sampling from depth of 12 cm

STUDIES OF TI-IE AVAILABILITY OF TOXIC HEAVY ELEMENTS

323

Bad

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,=

"7

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I
I=~176
i

~':.'.. $ /

investgaton

ql

l.::.: ~=_o,...,.,.
=lgo

Fig. 2. Situation of investigation area

soils were sampled at different depths. The distribution of elements in relation to the corresponding bulk concentrations is displayed for some of the elements in Fig. 4a and Fig. 4b. As shown by Fig. 4a, b the different sample populations are characterized by different predominances of element speciation. For instance, in the forest soils Zn is bound to phase 4 (Fe-ox.-hydrox.) and phase 6 (residual phase). In the slags, Zn is fixed predominantly to the sulfidic (5) and silicate phases (6). The Zn concentrations in the stream sediments are controlled by the carbonate (2) and easily reducible (3) phases. These findings indicate very different availabilities of the heavy elements with a sometimes increased hazard potential for substances with comparable low concentrations.

324
3589.200

O.W. ZACHMANN AND R. BLOCK

3589.400

3~11.000

~lmJlCO

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.

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2000

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samples

3000 4000

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1100, 1200, 1400: forest soil sampling points sampling A

0

6000 "~ 3: 7000 ~ P 800O o 9000 c

> 9000 O o

depth: - B - horizon h v 500 m

Fig. 3. Pb-distribution in forest soils near the lead smelting site

STUDIES OF THE AVAILABILITY OF TOXIC HEAVY ELEMENTS

325

forest 100 90: 807060~ 5040[ 302(1 10sample number

soils

slags

stream

sediments

!I

0+----

11 1= IGO

9 116

lO 9o 143/o 11122o

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sediments

satnpte number

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;~

(=,~mp~ depm - era)

14130 ( bulk r

adsorptive phase ~ Fe-ox.-hydmx. ph. ~

carbonatic ph. sulfidic phase

Mn-ox.-hydrox. ph. residual ph.

Fig. 4. (a) Sequential elution - distribution of element speciation (Zn, Pb)

326

13. W. ZACHMANN AND R. BLOCK

forest soils
I(90 90tO

slags

stream sediments

706040" 20"
10"

i~

umber
i;l
I 10

;2 328 214

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SOl ts

am

(=mmam G~=m~.r

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(bUk

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stream sediments

~=

4o-

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10 111 ~' na 47

11

17

44

(laJk cmemndQn

adsorptive phase i carbonattc ph. Fe-ox.-hydrox. ph. 17~ sulfldic phase

Mn-ox.-hydrox. ph. residual ph.

Fig. 4. (b) Sequential elution - distribution of element speciation (Cu, As)

STUDIES OF THE AVAILABILITYOF TOXICHEAVYELEMENTS

327

TABLE IV Mineralogical composition and concentrations of heavy elements (bulk analyses; #g/g) of the investigated stream sediments and slags sample mineral, Nr. compos.
a) stream IT 600 IT 512 IT 801 IT 805 sediments Q, Fs, M, K1 Q, S, C , K , I Q, O, C, K,I Q, O, C , G , I

heavy elements Zn Pb
125 9850 9330 5167

Cu

Cd
5 58 37 22

Ni
17 46 35 27

As
5 43 37 47

Se
0.7 3.5 0.5 0.7

1310 51 1 0 3 0 0 574 10380 680 1 4 1 3 0 550

b) slags S1 Olivine $2 Olivine

16370 5710 12220 6090

330 285

11 8

55 48

15 17

2.1 2.2

Abbreviations: Q - quartz, M - muscovite, O - olivine, C - cerussite, K calcite, S - sphalerite, I - illite, Fs - feldspar, K1- kaolinite, G - galena.

5. Results
In Table V the Pb concentrations eluted by BaC12 are compared to those eluted by the single steps of the sequential elution and the sums of elution steps (1 + 3), and (1 + 3 + 4). The Pb concentrations eluted by the BaCI2 solution fit the amounts released from the adsorptive phase (1), and the two oxidic phases (3, 4). Accordingly, the lead concentrations bound to phases 1, 3, and 4 are considered easily available. The mean of Pb released from phases 1, 3, and 4 is about 45% of the total Pb concentration of the forest soils. Allowing for the very high total concentration of Pb in the forest soils (up to 5%; Block, 1992), the area of the forest soils has to be considered as environmentally hazardous with a high contamination potential for plants and water (of. Table 5, last column). According to Dries (1987), the substitution of Fe and Mn by Pb is responsible for lead concentrations in Mn- and Fe-oxides and -hydroxides. However, due to the very different crystal radii of Pb 2+ (133 pm; Table VII) and Fe z+ (75 pm) and Mn 2+ (81 pm), Pb will not substitute Fe and Mn in their oxides and hydroxides. The generally easy availability indicates the predominance of the adsorptive bonding of lead to Fe-Mn-oxide-hydroxide (cf. Table V). The percentage of the Mn-oxide phase (elution phase 3) reaches only 1% of the Fe-oxide phase. However, the amounts of lead bound to the Mn-oxide phase sometimes exceed those bound to the Fe-oxide phase. This demonstrates the extreme importance of the Mn-oxide phase (X-ray amorphous) for the bonding of heavy elements as compared to the Fe-oxide phase.

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D.W. ZACHMANN AND R. BLOCK

TABLEV Comparison between Pb elutionby BaC12and sequential elutionfrom forest soils (in % of total concentration;relativestandard deviation of all elution procedures in the range of 2.1 - 4.4%; n = 3) Spl. Nr. BaClz sequentialdution(%) (%) steps
1 2 3 4 5 6

steps steps 1+3+4 1+3 1+3+4 in (%) (%) ~g/g 22 42 26 21 30 28 39 45 52 50 34 38 50 53 690 16200 1700 210 750 870 250

1100/12 1200/9 /25 /55 1400/8 /15 /40

43 58 48 45 43 43 56

11 39 21 21 15 16 25

51 40 43 53 58 46 41

11 3 5 15 12 14

23 10 24 13 8 12 14

1 4 1 3 1 1

3 4 6 10 3 5 5

Because lead shows a high tendency to form chloride complexes (Ball et aI., op cit.; Parkhurst et aI., 1980; Salomons and F6rstner, 1980), the BaC12 solution may extract higher amounts than the easily available concentrations (e.g. in elution step 4). However, even if the amount of available lead considered is restricted to the amounts obtained in phases 1 and 3 (20--40% of total lead), there are still very high amounts of available lead stored in the contaminated area. In Table VI the concentrations of Zn, Cu, and As eluted by the BaCI2 solution (easily available) are compared with those eluted in steps 1, 3, and 4 by the sequential elution. The comparison of the different elution procedures shows a distinct difference of the availability of Pb on the one hand, and Zn, Cu and As on the other hand. The bulk concentrations of Zn in the forest soils are small and the amounts bound to the adsorptive (1) and the easily reducible (3) phases are nearly negligible. As demonstrated by the BaC12 elution, the amounts of Zn eluted are also nearly negligible. Therefore, they fit best the amounts bound in phases 1 and 3 (Table VI). Probably, the prevailing soil pH of about 4 in the investigated area severely limits the fixation of Zn. The Zn amounts bound to the Fe-oxidic phase (4) were not released by the BaCI2 solution. Due to the small amount of the total Zn and the extremely small amounts of easily available Zn, under present conditions the contaminated area is not considered as an environmental hazard with regard to Zn. The radius of Zn 2+ (88 pro) allows the isomorphous substitution of Fe as well as of Mn in crystal structures. Whereas Pb is easily available from both oxide phases (Mn, Fe), Zn is bound with a high stability only to the Fe-oxide phase. The stable fixation of Zn by the Fe-oxidic phase during the BaCI2 elution fits the observations

STUDIES OF THE AVAILABILITY OF TOXIC HEAVY ELEMENTS

329

T A B L E VI C o m p a r i s o n o f elution of heavy metals from forest soils by BaC12 and sequential elution (in % of total concentrations; relative standard deviation of all elution procedures in the range o f 2.1-4.4%; n = 3) Elem. Spl.Nr./ depth BaC12 (%) sequ. elution (%) steps available '~ (#g/g)

1
Zn 1100/12 1200/9 /25 /55 1400/8 /15 /40 Cu 1100/12 1200/9 /55 1400/8 /15 /40 4 19 3 2 3 5 3 7 7 20 32 7 4 steps 1 2

1,3
10 1 1 4 3 13 26 2 -

1,3,4
24 50 28 34 24 30 28 76 79 73 60 61 70 4 1 15 1 1l 1 l 2

l
As 1100/12 1200/9 1200/25 1400/8 /15 /40 4 . 1 . 1 . 5 .

1,3
10 42 18 24 0.07 0.20

Calculated from bulk concentrations (c.f. Table IV) and percentages eluted by steps: - Zn, Cu: steps 1 + 3; - As: step 1.

T A B L E VII Crystal radii of cations considered in this study; data according to Shannon (1976); radii in p m (10 -12 m); the ionic radii are given for sixfold coordination cation radiu Fe 3+ 69 Fe 2+ 75 Mn 3+ 72 Mn 2+ 81 Pb 2+ 133 Zn 2+ 88 Cu z+ 87 As 3+ 72 As 5+ 60

330

D.W. ZACHMANN AND R. BLOCK

reported by Brtimmer et aI. (1986), according to which Zn is released only after digestion of the oxides. However, considering the crystal radii it is not quite evident why Zn should not be fixed in the Mn-oxide phase (cf. Cu). The very small bulk concentrations of Zn in the soils of the investigated area do not allow a conclusive answer for the moment. The radius of Cu is similar to that of Fe and Mn and may replace both isomorphically in lattices. Similar to Zn, the adsorptively bound Cu percentages (phase t) are relatively small. However, the amounts of Cu bound to the Mn oxide phase are not negligible (cf. Table VI). As demonstrated by the BaC12-elution, this Cu percentage is easily available without digestion of the Mn-oxidic phase. Similar to Zn and in contrast tot Pb, Cu was found to be not easily available from the Fe-oxide phase. According to McLarean et al. (1983), Cu is not easily available from the oxide phases. However, this statement should be restricted to the Fe-oxide phase. Due to the ease of volatilization during smelting processes, high (bulk) amounts of As should be expected in the environment of the Bleihtitte smelting site. The occurrence of high amounts of As in the Bleihtitte area are documented in the stream sediments. However, the volatilization of As from soils by methylation is a well known process (Andreae, 1986; McBride et al., 1978; Vahter and Marafante, 1988) and therefore, the potentially high amount of As can no longer be found in the forest soils. The concentrations of easily available As (elution phase 1) are negligible. The crystal radii of As 3+ and As 5+ allow the isomorphical replacement of Fe and Mn in the oxide phases. According to these conditions, As is bound with a high stability in the Mn-oxide phase and especially'in the Fe-oxide phase of the stream sediments and slags (cf. Fig. 4a and 4b). From both phases it is not extracted by the BaCI2 solution. This finding fits the well known fact that Fe-As compounds may show a very high stability. For instance, Fe(AsO4) 92H20 (skorodite) is extremely stable and therefore proposed as a possible form of detoxication of hazardous As compounds (Heinisch et al., 1985).

6. Summary and conclusions

The comparison of both elution methods shows a good coincidence of the bulk concentrations (especially Pb) eluted by the BaCI2 solution and the concentrations of some bonding forms extracted by the sequential elution (cf. Table V and VI). The comparison of the results of both procedures allows for a more precise definition of the easily available bonding forms in polluted soils. Based on this study, the results of the sequential elution may be used with more significance for the prognosis of hazards in the environment. Heavy metals from the following bonding forms may be generally available in natural environments without change of the soil pH: - adsorptive bonding

STUDIES OF THE AVAILABILITYOF TOXICHEAVYELEMENTS

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TABLE VIII Availability of Pb, Cu, Zn, and As from the single bonding forms (X = easily available) elutionphase 1 2 3 bonding form adsorptive Mn-ox.-hydrox. Fe-ox.-hydrox. Pb X X X Zn X X Cu X X As X

bonding by Mn- and Fe-oxide-hydroxides

However, the availability of different elements in the very same bonding form varies significantly. Generally, all elements bound to the adsorptive phase (1) are easily available. The proportions bound to the Mn- (3) and Fe-oxide (4) phases show different stabilities. Pb is easily available from all three phases (1, 3, 4). Zn and Cu are fixed by the Fe-oxide phase but not by the Mn-oxide phase, whereas As is fixed by both oxide phases. Therefore, As shows the smallest availability. The findings are summarized in Table VIII. The table shows that the potential of the forest soil elements to pollute the environment in downstream areas is as follows: Pb > Cu = Zn > As. The reasons for the different reactions to leaching processes can generally be found in the similarity of the crystal radii of heavy elements as compared to Fe and Mn. Based on the findings in the contaminated soils, the hazardous potential of the stream sediments and slags in the Bleihtitte area (Clausthal-Zellerfeld, Upper Harz Mountains) is given in Table IX. As demonstrated by Tables V and IX, the contaminated forest soils and slags in the Bleih~itte area, and the Innerste sediments must be considered as an environmental risk for the downstream areas. The hazardous potential is characterized by high amounts of easily available Pb concentrations in the forest soils; high amounts of easily available Pb, Zn and Cu (partially) in stream sediments and slags. The application of comparing elution procedures allows a more precise diagnosis of the hazardous potential of heavy elements in forest soils. The release of Mn and Fe from stream sediments shows the same characteristics as from forest soils (Fig. 4). Therefore, the results of this study are believed to be transferable to other substances. The estimate of the availability of heavy elements from other substances, e.g. mineral wastes of the industry (filter dusts, wastes of the desulfurication of fumes, etc.) requires similar investigations as described in this study.
-

332

D. W, ZACHMANN AND R. BLOCK

TABLE IX Easily available amounts of heavy elements in stream sediments and slags (ppm; in brackets: percentageof total amount - cf. Table III and IV) Sample Pb Zn Cu As 0.07(1.5) <.01(-) <.01(-) <.01(-)

a) straem sediments (Innerste river) IT 600 580(44) 5(4) i0(5) IT 512 2940(29) 1420(14) .4(1) IT 801 4910(47) 3200(34) 88(13) IT 805 4690(33) 2070(40) 180(32) b) Slags (Bleihlitte smelting site) S1 2340(41) 1060(7) $2 2510(41) 970(8)

5(.1.5) 0.86(5.5) 5(1.8) 0.41(2.5)

Many of the investigated materials show very high amounts of toxic elements bound as carbonates, especially lead. Under the aspect of decreasing soil pH, this element speciation must be considered as another hazardous potential for the contamination of downstream areas.

Acknowledgements
Parts of this study were supported by a grant of the Volkswagen Foundation (Z.). We would like to thank the staff of the Geochemical Laboratory for their analytical help (S. Schefler, R. L6hr, O. Ewald). We are grateful to J. Johannsen for her assistance in correcting the manuscript.

Appendix: Analytical procedures

The analytical procedures used follow the methods as described by the German Industrial Norms (DIN) DIN 19 684-8: Determination of the cation exchange capacity of soils and of exchangeable cations. 5 g of air-dried fine soil is filled in a funnel between two layers of quartz sand. 40 ml of a solution with 25 g BaCI2 96H20/1000 ml (pH = 7) is poured three times into the funnel at intervals of at least I hour. After about 15 hours, 100 ml of distilled water is poured into the funnel. The cations are analyzed in the combined elutions. DIN 38 414-4: Determination of substances eluted by water from slurries and sediments.

STUDIES OF THE AVAILABILITY TOXICHEAVYELEMENTS OF

333

A sample a m o u n t equivalent to 100 g of air-dried material is placed in a flask with a v o l u m e o f 2,000 ml. 1 1 o f distilled water is added. The flask is carefully shaken for 24 hours. The solution is filtratred (45 # m ) before the analytical determination. D I N 38 414-7: Digestion of slurries and sediments by aqua regia. 3 g o f dried and ground sample material is placed into a reaction vessel. 21 ml HC1 (37%) and 7 ml HNO3 (67%) are added. A reflux cooler and an adsorption vessel (10 ml HNO3) are m o u n t e d onto the reaction vessel. After some hours o f predigestion at r o o m temperature the mixture is heated for two hours. The solution o f the adsorption vessel is poured through the cooler into the reaction vessel. The adsorption vessel and cooler are rinsed several times with HNO3 and water. The c o m b i n e d solutions are analyzed for h e a v y elements.

References
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